RSS-Feed abonnieren
Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.
https://www.thieme-connect.de/rss/thieme/de/10.1055-s-00000083.xml
Synlett 2005(5): 0713-0731
DOI: 10.1055/s-2005-864793
DOI: 10.1055/s-2005-864793
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York
Mechanistic Studies in Triazolinedione Ene Reactions
Weitere Informationen
Received
11 August 2004
Publikationsdatum:
09. März 2005 (online)
Publikationsverlauf
Publikationsdatum:
09. März 2005 (online)
Abstract
Triazolinediones react with olefins bearing allylic hydrogens in an ene fashion to afford N-allylurazoles. This reaction, apart from considerable mechanistic attention, shows also substantial synthetic utility. Extensive experimental data, such as deuterium kinetic isotope effects, trapping of intermediates, and stereochemical studies, and to a lesser extent computational work, support a two-step mechanism with irreversible formation of a three-membered ring intermediate (aziridinium imide). On the basis of recent experimental and theoretical work, an open biradical has been proposed as the key intermediate.
1 Introduction and Background
2 Isotope Effects
3 Regioselectivity and Diastereoselectivity Studies
3.1 Regioselectivity
3.1.1 Regioselectivity with Simple Alkenes
3.1.2 Regioselectivity with Substituted Alkenes, Styrenes, α,β-Unsaturated Esters, Carbonyl Compounds and Sulfoxides
3.2 Diastereoselectivity
4 Solvent Trapping Studies
5 Stereochemistry: Simple Alkenes, Non-Polar Solvents
6 Theoretical Calculations
7 Concluding Remarks
Key words
ene reactions - regioselectivity - diastereoselectivity - stereochemistry - kinetic isotope effects
- 1
Moody CJ. Adv. Heterocycl. Chem. 1982, 30: 1 ; and references therein - 2
Pirkle WH.Stickler JC. J. Chem. Soc., Chem. Commun. 1967, 760 - 3
Koerner v Gustorf E.White DV.Kim B.Hess D.Leitich J. J. Org. Chem. 1970, 35: 1155 - 4
Gilis BT.Hagarty JD. J. Org. Chem. 1967, 32: 330 -
5a
Wagener KB.Turner SR.Butler GB. J. Polym. Sci., Part B 1972, 10: 805 -
5b
Butler GB.Williams AG.Leong K. Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem. 1977, 18: 843 - 6
Corey EJ.Snider BB. J. Org. Chem. 1973, 38: 3632 -
7a
Snider BB.Corcoran RJ.Breslow R. J. Am. Chem. Soc. 1975, 97: 6580 -
7b
Breslow R.Corcoran RJ.Snider BB.Doll RJ.Khanna PL.Kaleya R. J. Am. Chem. Soc. 1977, 99: 905 - 8
Pavey JBJ.Lawreence AJ.Potter AJ.Cosstick R.O’Neil IA. Tetrahedron Lett. 1998, 39: 6967 - 9
Adam W.Pastor A.Wirth T. Org. Lett. 2000, 2: 1295 - 10
Adam W.Degen HG.Krebs O.Saha-Möller CR. J. Am. Chem. Soc. 2002, 124: 12938 - 11
Baran PS.Guerrero CA.Corey EJ. J. Am. Chem. Soc. 2003, 125: 5628 - 12
Baran PS.Guerrero CA.Corey EJ. Org. Lett. 2003, 5: 1999 - 13
Seymour A.Greene FD. J. Am. Chem. Soc. 1980, 102: 6384 - 14
Orfanopoulos M.Smonou I.Foote CS. J. Am. Chem. Soc. 1990, 112: 3607 - 15
Orfanopoulos M.Stratakis M.Elemes Y.Jensen F. J. Am. Chem. Soc. 1991, 113: 3180 - 16
Elemes Y.Foote CS. J. Am. Chem. Soc. 1992, 114: 6044 - 17
Clennan EL.Koola JJ. J. Am. Chem. Soc. 1993, 115: 3802 - 18
Smonou I.Khan S.Foote CS.Elemes Y.Mavridis IM.Pantidou A.Orfanopoulos M. J. Am. Chem. Soc. 1995, 117: 7081 - 19
Stratakis M.Orfanopoulos M.Foote CS. J. Org. Chem. 1998, 63: 1315 - 20
Vassilikogiannakis G.Stratakis M.Orfanopoulos M.Foote CS. J. Org. Chem. 1999, 64: 4130 - 21
Chen JS.Houk KN.Foote CS. J. Am. Chem. Soc. 1997, 119: 9852 - 22
Grdina MB.Orfanopoulos M.Stephenson LM. J. Am. Chem. Soc. 1979, 101: 3111 - 23
Nelsen SF.Kapp DL. J. Am. Chem. Soc. 1985, 107: 5548 - 24
Squillacote M.Mooney M.De Felipis J. J. Am. Chem. Soc. 1990, 112: 5364 - 25
Poon THW.Park S.Elemes Y.Foote CS. J. Am. Chem. Soc. 1995, 117: 10468 - 26
Adam W.Carballeira N. J. Am. Chem. Soc. 1984, 106: 2874 - 27
Singleton DA.Hang C. J. Am. Chem. Soc. 1999, 121: 11885 -
28a
Melander L.Saunders WH. Reaction Rates of Isotopic Molecules Wiley-Interscience; New York: 1980. -
28b
Carpender BK. Determination of Organic Reaction Mechanism John Wiley; New York: 1984. - 29
Cheng CC.Seymour CA.Petti MA.Greene FD. J. Org. Chem. 1984, 49: 2910 - 30
Orfanopoulos M.Foote CS.Smonou I. Tetrahedron Lett. 1987, 28: 15 - 31 The reversible formation of an analogous three-membered ring intermediate (aziridine N-oxide) has been recently reported for the nitrosoarene ene reaction:
Adam W.Krebs O.Orfanopoulos M.Stratakis M.Vougioukalakis GC. J. Org. Chem. 2003, 68: 2420 - 32
Elemes Y.Orfanopoulos M. J. Am. Chem. Soc. 1992, 114: 11007 -
33a
Stephenson LM.Grdina MJ.Orfanopoulos M. Acc. Chem. Res. 1980, 13: 419 -
33b
Stratakis M.Orfanopoulos M. Tetrahedron 2000, 56: 1595 -
34a
Ohashi S.Leong KW.Matyjaszewski K.Butler GB. J. Org. Chem. 1980, 45: 3467 -
34b
Ohashi S.Butler GB. J. Org. Chem. 1980, 45: 3472 - 35
Elemes Y.Stratakis M.Orfanopoulos M. Tetrahedron Lett. 1989, 30: 6903 - 36
Orfanopoulos M.Elemes Y.Stratakis M. Tetrahedron Lett. 1990, 31: 5775 - 37
Houk KN.Williams JC.Mitchell PA.Yamaguchi K. J. Am. Chem. Soc. 1981, 103: 949 - 38
Clennan EL.Chen X.Koola JJ. J. Am. Chem. Soc. 1990, 112: 5193 - 39
Elemes Y.Stratakis M.Orfanopoulos M. Tetrahedron Lett. 1997, 36: 6437 - 40
Gopalan A.Moerck R.Magnus P. J. Chem. Soc., Chem. Commun. 1979, 548 - 41
Adam W.Schwarm M. J. Org. Chem. 1988, 53: 3129 - 42
Stratakis M.Hatzimarinaki M.Froudakis GE.Orfanopoulos M. J. Org. Chem. 2001, 66: 3682 - 43
Alberti MN.Vougioukalakis GC.Orfanopoulos M. Tetrahedron Lett. 2003, 44: 903 - 44
Shiloff JD.Hunter NR. Tetrahedron Lett. 1976, 3773 - 45
Hoye TR.Bottorff KJ.Caruso AJ.Dellaria JF. J. Org. Chem. 1980, 45: 4287 - 46
Akasaka T.Misawa Y.Goto M.Ando W. Tetrahedron 1989, 45: 6657 - 47
Vassilikogiannakis G.Stratakis M.Orfanopoulos M. Org. Lett. 2000, 2: 2245 - 48
Matsson O.Westway KC. Adv. Phys. Org. Chem. 1996, 31: 143 - 49 For a review on the diastereoselectivity of singlet oxygen ene reaction see:
Prein M.Adam W. Angew. Chem., Int. Ed. Engl. 1996, 35: 477 - 50
Stratakis M.Vassilikogiannakis G.Orfanopoulos M. Tetrahedron Lett. 1998, 39: 2393 - 51
Adam W.Nestler B.Pastor A.Wirth T. Tetrahedron Lett. 1998, 39: 2625 - 52
Peters K.Peters E.-M.Adam W.Nestler BZ. Kristallographie 1998, 213: 305 - 53
Gau A.-H.Lin G.-L.Uang B.-J.Liao F.-L.Wang S.-L. J. Org. Chem. 1999, 64: 2194 - 54
Adam W.Bottke N.Krebs O.Lykakis I.Orfanopoulos M.Stratakis M. J. Am. Chem. Soc. 2002, 124: 14403 -
55a
Adam W.Wirth T.Pastor A.Peters K. Eur. J. Org. Chem. 1998, 501 -
55b
Adam W.Bosio SG.Gegen H.-G.Krebs O.Stalke D.Schumacher D. Eur. J. Org. Chem. 2002, 3944 - 56
Jensen F.Foote CS. J. Am. Chem. Soc. 1987, 109: 6376 - 57
Clennan EL.Earlywine AD. J. Am. Chem. Soc. 1987, 109: 7104 - 58
Smonou I.Orfanopoulos M.Foote CS. Tetrahedron Lett. 1988, 29: 2769 - 59
Elemes Y.Orfanopoulos M. Tetrahedron Lett. 1991, 32: 2667 -
60a
Stephenson LM.McClure DE.Sysak PK. J. Am. Chem. Soc. 1973, 95: 7888 -
60b
Orfanopoulos MG.Stephenson LM. J. Am. Chem. Soc. 1980, 102: 1417 - 61
Vassilikogiannakis G.Elemes Y.Orfanopoulos M. J. Am. Chem. Soc. 2000, 122: 9540 - 62 For a review on computational studies concerning ene reactions of singlet oxygen RTADs and nitroso compounds see:
Leach AG.Houk KN. Chem. Commun. 2002, 1243